Dyestuffs containing sulphur and process of making same



Fatented dune ll. lh h QTATpgg AND @ll i No i lrawln e.

To all who m, 5t may concern:

Be -it known that we, Rroemno lllnnz a Prussian subject, residing at Frankforton-the-h lain, Germany, Eysseneclrstrasse 17., and Nonnnnr S'rnionn, a suloject ot the Czechoslovakian Republic, residing at lFechenheiin, near Franhfort-onthe-Main, Germany, Langstrasse 4L1. have invented certain new and useful lmprovenients in Dyestuffs Containing Sulphur and Processes of Making Same, of which the following is a full description.

We have found that new and very valuable dyestutls are obtained Toy treating (l-oxynaphthoquinonearylimino compounds of the following general formula turic acid-to act on the a ove-named compounds.

The addition of a catalyzer acts in some cases favorably.

The new dyestuffs thus obtained probably contain in their molecule the thlazinenuth f l Glens and Possess e 01 owmg general kilos of naphthalene and 0.2 kilos of iodide formula Application filed hepteinher 1, Elttil.

Serial course.

because, as we have found. the same dyestuhts are obtained by condensing suitable sulturized arylarnines, having the sulphur or the sulphur containing" group in the orthoposition to the amino group, with (i-naphthoquinone or with a derivative or sultonic acid thereof.

For instance, the dyestuil obtained hy treating {l-onynaphthoquinoneanilide with sulphur, or with a solution of sulphur in chloridesot sulphur has been found identical with that produced by condensing oarninothiophenol with [inay ilutlroquinone or 3.4,dichlor fi-naphthoquinone. (Ainnalen der @hemie 283. page E l-7.)

The new dyestutlis belong to the class of chromium inordant dyestulls and produce it dyed and printed in the usual manner for this class of dyestuffs hright green, to greenish hlaclr, to hlaclr shades of excellent fastness. V i

Those which do not contain acid groups sulfonic' acid or carhoxylic acid groups) in their molecule may also be advantageously dyed in the vat and then developed by an after-treatment with suitable metallic salts,

preferably chromium salts, into fast green 1 to blaclr shades."

The following examples illustrate our invention: 7

Example J.-l0 kilos of the dry product of condensation of p.toluidine with 0: 5 naphthoquinone a sulfonic acid having the formula: I I

are mixed with 20 kilos ofQsulphur,

thalene is first removed or example, by

extracting the melt with hotsolvent naphtha) and then the superfluous sulphur,

for" example by digesting the residue with I dissolved in concentrated sulfuric acid, and

v vat.

this solution is then poured on to ice, filtered, washed until it is neutral. It is thus obtained in a very finely divided paste and may then be dyed or printed either in the manner customary for mordant dyestuffs on chrome mordanted WOOl or cotton, producing thus fast bluish green shades, or it may also be advantageouslydyed from the In an alkaline hydrosulfite solution it is readily soluble to a yellow colored vat and dyes Wool from such a vat dark violet shades which turn to claret red on acidifying and to fast bluish green by an aftertreatment with chromium salts in an acid bath.

In a dry state the dyestufi' represents a violet powder insoluble in water, sparingly soluble with a red violet color in benzene and chloroform, dissolving with a dark violet color in concentrated sulfuric acid, which solution turns to green by the addition of a little water, whereas by diluting with more water the color is precipitated in red violet flakes. By warming the dyestufi with fuming sulfuric acid until a test becomes soluble in water it is sulfonated and the sulfonic acid thus produced may be separated by pouring the solution on to ice, filtering and washing with a dilute salt solution until it is neutral. If dyed or printed in the manner usual for acid dyeing, chromium mordant dyestuffs of fast bluish green shades are obtained.

Very similar coloring matters are produced if the products of condensation of 0: 6 naphthoquinone or, sulfonic acid with aniline o. m. p. chloraniline-o. n1. toluidine, p. anisidine and p. phenitidine are treated as above described.

Example f2.10 kilos of the product of condensation of Example 1, (of 0: 5 naphthoquinone a sulfonic acid with p. toluidine) are introduced at ordinary temperature whilst stirring into a mixture of 80 kilos of glacial acetic acid and a solution of 8 kilos of sulphur in about 30 kilos of sulphurchloride or disulphurdichloride. The reaction at once commences and is completed without the application of external heat after some hours stirring; The separated dyestuif is filtered off and purified, if necessary, by digesting 'it with a concentrated solution of sodium sulphide.

It is also preferable to convert it into a finely divided paste as described in the foregoing example;

It appears to-l'be identical with-the dyestufi' produced according to Example 1 and it may be used for dyeing and printing purposes in the same manner as this. If the produce of condensation of p. anisidine with the a t, naphthoquinone a sulfonic acid (having the formula is treated with a solution of sulphur in chlo ride of sulphur as described above, then a dyestutf is obtained dyeing wool from the vat violet shades which turn to a brilliant yellowish green by an aftertreatment with sodium bichromate in an acid bath; these latter dyeings are distinguished by their excellenlt fastness to washing, milling, potting and i it.

[:"rmmple 3.8 kilos of sulfur are gradually introduced whilst stirring into 200 kilos of fuming sulfuric acid of about 30% S0 at a temperature from 20-30 C. As soon as the sulphur is dissolved, 10 kilos of the roduct of condensation of p. toluidine wit 0:,[5 naphthoquinone-oz sulfonic acid are added and stirring is continued for some time at 3O L0 C. \Vhen the reaction is complete, the whole mass is poured on ice, the separated dyestufi is filtered and washed until it is neutral preferably with a dilute salt solution. Besides the formation of the thiazinenucleus in this case a sulfonation of the coloring matter has taken place and an acid dyeing mordant dyestufi' is obtained. It produces on chrome mordanted wool or if dyed in an acid bath and aftertreated with chromiumsalts fast bright green shades. Full green to greenish black acid dyeing mordant dyestuffs are produced if the products of condensation of 0: 5, naphthoquinonecz sulfonic acid with amidosalicylic acid or amidocresotinic acid are treated with sulphursesquioxide in a manner similar to that above described.

The product of condensation of p. nitraniline with B napththoquinone 4.6 disulfonic acid if treated with a solution of sulphur in fuming sulfuric acid as described in this example produces an acid dyeing mordant dyestufi with sulphur substantially as described.

2. The process of manufacturing new mordant dyestufis containing in their molecule the thiazine nucleus'wh-ich consists in lid treating an 'oxynaphthoquinonear limino compound of the following general ormula R-Ar i) with sulphur in a diluent for sulphur sub- .stantially as described.

3. The process of manufacturing new mordant dyestuffs containing in their molecule the thiazine nucleus which consists in treating an oxynaphthoquinonearylimino compound of the following general ztormula (R==A 1 v I f W) molecule the thiamine nucleus obtainableby treating an oxynaphthoquinonea'r limino compound of the lt'ollowing general ormula (R Aryi) i o with sulturizingagents, said dyestus be ing in a dry state violet to dark blue colored powders, sparingly soluble in most of the organic solvents, soluble in concentrated sulfuric acid with a brown to violet to a blue color which by the addition of a little water turns to a bright green color and by diluting with more water to a claret red color, and producing fast green; reenish black to black shades it dyed or printed in the manner usual for chromium mordan-t dyestuffs, or if dyed in the vat and aftertreated With chromium salts in an acid bath.

5. As a new product the hereinbefore described new mordant dyestud derived from (5 oxynaphthoquinone .toluid by treating itwith a solution of su phur in fumin sulfuric acid, being a sultonic acid 0 the thiazine dyestufi' of the following probable formula CHO said dyestufl" being in" a dry state a dark blue powder soluble with a claret red color in water, which color turns to a dark bluish green by the addition of an alkali, sparingly soluble with a claret red and acetone, soluble with an olive brown color in concentrated'sulfuric acid, which color turns to a bright green by the addition of a little water and to claret red by adding more water, and'producing, when dyed or printed in the manner usual for acid dyeing chromium mordant dyestufi's, bright bluish green shades which are distinguished by their fastness to washing, milling, potting and light.

6. As a new article ot manufacture the v hereinbetore described new mordant dyecolor in alcohol ltlll stulli derived from (5 oxynaphthoquinone p..-

oxyalkylanilid tion of sulphur in chlorides out sulphur, having probably the following constitutional formula said dyestufit' being in a dry state let powder, sparingly soluble in the usual 1: anic vsolvents, soluble with a claret red cofiir in hot nitrobenaene, soluble with a by treating it with a solua red viellll llli

blue-grhn color in concentrkted sulfuric 1921; in the presenoe of two subscribing acid and forming with alkaline hydrosulwitnesses. 1 fite a ellow vat from which wool is dyed in RICHARD HERZ PH. D.

blue s ades which turuto fast bright green NORBERT sTEIER, PH. D. 5 if aftertreated with chromium salts. Witnesses:

In witness whereof we have hereunto JACOB SOHWEIGHOFER, signed our names this 16th day of August, GUSTAV CLfiNER. 

